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<strong>Arab</strong> <strong>Journal</strong> <strong>of</strong> <strong>Nuclear</strong> <strong>Sciences</strong> <strong>and</strong> <strong>Applications</strong>, 45(2)169-178 (2012)<br />
Bioleaching <strong>of</strong> Uranium - bearing material from Abu Thor area, West<br />
Central Sinai, Egypt for recovering uranium.<br />
Galal Mahmoud AbdEl Wahab , Maisa Mohamed Amin <strong>and</strong> Sami Kotb Aita<br />
<strong>Nuclear</strong> Materials Authority, P.O. Box 530 El Maadi, Cairo, Egypt.<br />
Rona82007@gmail.com<br />
ABSTRACT<br />
A uranium-bearing material was recorded within the Intra-Carboniferous<br />
Paleokarst Pr<strong>of</strong>ile <strong>of</strong> Um-Bogma Formation at Abu Thor area, West Central Sinai,<br />
Egypt. The present paper is concerned with the bioleaching <strong>of</strong> U <strong>and</strong> Cu using<br />
Aspergillus Niger (A. Niger) followed their proper recovery. The working Abu Thor<br />
representative sample assays 0.22% U as the element <strong>of</strong> interest as well as up to 25% CuO<br />
beside the other rock constituents SiO2 (33%), Al2O3 (10.4%) <strong>and</strong> CaO(8.5%). The effective<br />
bioleaching <strong>of</strong> U <strong>and</strong> Cu from Abu Thor ore sample using A.Niger was performed at the<br />
following optimum conditions: an incubitation time <strong>of</strong> 6 days, sample/ liquid (S/L) ratio <strong>of</strong><br />
1/10, pH value <strong>of</strong> 1 <strong>and</strong> a temperature <strong>of</strong> 60 º C.<br />
The prepared bioleach liquor assays 0.19 g/l <strong>of</strong> U <strong>and</strong> 15.8 g/l <strong>of</strong> Cu with leaching<br />
efficiencies <strong>of</strong> 97% <strong>and</strong> 79%, respectively. Uranium was recovered using 25% TBP in<br />
kerosene at O/A ratio <strong>of</strong> 1/1 <strong>and</strong> contact time <strong>of</strong> 5 min with achieved extraction<br />
efficiency <strong>of</strong> 96%. However the stripping <strong>of</strong> U was conducted by using 8% Na2CO3 at<br />
A/O ratio <strong>of</strong> 1/1 <strong>and</strong> contact time <strong>of</strong> 5 min with stripping efficiency reached 99%. On<br />
the other h<strong>and</strong>, Cu was directly precipitated as CuS using the freshly released H2S gas<br />
with the addition <strong>of</strong> solid Na2S. The optimum precipitation conditions were S/L ratio <strong>of</strong><br />
1/100, pH1.5 <strong>and</strong> room temperature where the precipitation efficiency <strong>of</strong> Cu achieved<br />
99%.<br />
1-INTRODUCTION<br />
The origin <strong>of</strong> uranium mineralization <strong>of</strong> Um-Bogma Formation in West Central Sinai was<br />
reported by many authors the most important <strong>of</strong> them: Hilmy <strong>and</strong> Mohsen, (1965) (1) , El Reedy et<br />
al.,(1988) (2) , Dabbour <strong>and</strong> Mahdy, (1988) (3) , El-Sharkawi et al., (1990b) (4) , Hussein et al., (1992)<br />
(5) , Aita, (1996) (6) <strong>and</strong> Abd El Moneim et al., (1997) (7) . Recently Mira <strong>and</strong> Aita, (2009) (8)<br />
postulated that, the Carboniferous stratabound U <strong>and</strong> Cu mineralization in the form <strong>of</strong> copper<br />
carbonate, chloride, silicate, sulfate <strong>and</strong> phosphate minerals <strong>of</strong> super gene origin has been<br />
concentrated by pedogenic processes <strong>and</strong> latosol formation.<br />
Bioleaching processes are the ability <strong>of</strong> microorganisms (bacteria <strong>and</strong> fungi) to transform solid<br />
compounds into soluble <strong>and</strong> extractable elements <strong>and</strong> which can then be easily recovered.<br />
Bioleaching <strong>and</strong> bio-oxidation processes have been commercially applied for the recovery <strong>of</strong> copper,<br />
gold <strong>and</strong> uranium for two decades. In the near future, Turkish copper, gold <strong>and</strong> uranium mines will<br />
probably use these processes as commercial applications due to the economical <strong>and</strong> environmental<br />
reasons. In addition to lab tests, full scale feasibility studies to determine the impacts <strong>of</strong> climate <strong>and</strong><br />
environmental factors for potential bioleaching in the mining areas will also be completed in the near<br />
future (Akcill, 2004)<br />
-169-<br />
(9) .<br />
Bioleaching is a new trend for leaching <strong>and</strong> processing operations <strong>of</strong> ground ore. These trends are<br />
likely to continue as new techniques <strong>and</strong> are developed in the future depending <strong>of</strong> course on the type<br />
<strong>and</strong> grade <strong>of</strong> the deposits as well as the uranium price. A. Niger is one <strong>of</strong> the most widely used fungi<br />
in the bioleaching applications <strong>and</strong> has many advantages over bacterial leaching, including the ability<br />
to grow under higher pH <strong>and</strong> faster leaching rate. This fungus has also been used in the production <strong>of</strong>
<strong>Arab</strong> <strong>Journal</strong> <strong>of</strong> <strong>Nuclear</strong> <strong>Sciences</strong> <strong>and</strong> <strong>Applications</strong>, 45(2)169-178 (2012)<br />
organic acids as citric, oxalic, acetic <strong>and</strong> glycolic acids (Gu <strong>and</strong> Wong, 2007) (10) . Organic acids are<br />
well known lixiviates for bioleaching <strong>of</strong> heavy metals from ore materials <strong>and</strong> solid wastes (Hefnawy<br />
et al., (2003) (11) , Mulligan et al.,2004) (12) . A. Niger was effectively used in U <strong>and</strong> Cu leaching <strong>of</strong> the<br />
Gibbsite minerals collected from west central Sinai, Egypt <strong>and</strong> assayed 0.12% <strong>of</strong> U <strong>and</strong> 0.7% <strong>of</strong> Cu.<br />
The maximum leaching efficiencies were 82 <strong>and</strong> 76%, respectively at the optimal conditions,<br />
(Yossef, 2007) (13) .<br />
Several studies have been published about the recovery <strong>of</strong> U from different ore materials<br />
especially from Sinai area these include: Amer, (1997) (14) who has been able to recover 99% <strong>of</strong> U<br />
from the sulfate leach liquor <strong>of</strong> the uraniferous Paleozoic sedimentary rocks <strong>of</strong> Abu Thor area<br />
assayed 0.312% <strong>of</strong> U using Trioctyl amine, (TOA) organic solvent. Cecal et al., (2005) (15) studied<br />
the feasibility <strong>of</strong> bacterial recovery <strong>of</strong> U from the low grade black schist's occurring in the Okcheon<br />
district, South Korea. Following the introduction <strong>of</strong> Acidithiobacillus ferrooxidans, 80% <strong>of</strong> U could<br />
be extracted from the schists, which contain 0.01% U3O8 by weight, within 60 h at a pulp density <strong>of</strong><br />
100 g-ore/l. Only 18% <strong>of</strong> U was extracted without the microbial activity. Uranium leaching<br />
efficiency was not greatly affected by the addition <strong>of</strong> Fe 2+ in the range <strong>of</strong> 5–9 g/l, <strong>and</strong> the leaching<br />
efficiency <strong>of</strong> U from this schist’s by A. ferrooxidanscould can be efficiently maintained at high pulp<br />
densities (up to 500 g-ore/l).<br />
In the present work, a new technique has been performed depending mainly upon precipitation<br />
<strong>of</strong> the main interfering elements such as: Zn, Pb <strong>and</strong> Cu directly using freshly prepared H2S gas. The<br />
bioleach liquor free <strong>of</strong> these interfering elements was then directly subjected to precipitation using<br />
NaOH at pH11 <strong>and</strong> the obtained precipitate was dissolved with 3% HNO3 solution to be suitable for<br />
the recovery <strong>of</strong> pure U salt using TBP.<br />
2-EXPRIMENTAL<br />
2.1. Sampling<br />
A representative sample weighting 50Kg was collected from the upper organic -rich mudstone<br />
sub horizon <strong>of</strong> the latosol horizon <strong>of</strong> Abu Thor area by Mira <strong>and</strong> Aita, (2009) (8) according to the<br />
geological map shown in Figure (1). The collected sample consists mainly <strong>of</strong> alternating multi<br />
colored layers <strong>of</strong> kaolinitic black to green shale, ochres <strong>and</strong> nodules <strong>of</strong> alunite <strong>and</strong> gypsum together<br />
with the copper <strong>and</strong> uranium minerals. The later are mainly present as lenticular masses <strong>of</strong> up to<br />
40cm long <strong>and</strong> 10cm thick as well as discrete pockets up to 20cm in diameter beside some streaks,<br />
veinlets <strong>and</strong> spots that are also recorded.<br />
2.2. Materials <strong>and</strong> Sample Characterization.<br />
A. Niger was isolated from the black shale ore in Wadi Nasib area, South Western Sinai, Egypt<br />
<strong>and</strong> used in the bioleaching <strong>of</strong> the ore sample . The medium used was Dox liquid <strong>of</strong> the following<br />
composition (g/l):1NaNO3, 2 KH2PO4, 1Mg SO4.7 H2O, 0.5 KCl, 0.5 FeSO4.5 H2O <strong>and</strong> trace <strong>of</strong><br />
sucrose. The pH value <strong>of</strong> the medium was adjusted at 6.5 before autoclaving at 1.5 atmospheres. for<br />
20 min. A weight <strong>of</strong> 0.5g <strong>of</strong> the ore sample ground to a particle size less than 0.25mm was<br />
completely dissolved by using the acid mixture (H2SO4, HCl <strong>and</strong> HF) <strong>and</strong> directed to different<br />
analysis methods for determining its chemical composition. Both the major elements (Cu, Al, Zn, Fe)<br />
<strong>and</strong> the trace elements (Mn, V, Pb) were determined using the flame atomic absorption, (FAA)<br />
Unicam 969 at the proper wavelengths. While U was analyzed by titration against NH4VO3 (Daveis<br />
<strong>and</strong> Gray, 1964) (16) , Si was analyzed by UV spectrophotometer at ?640nm with molibedate method.<br />
The flame photometer (Sherwood Model 410) was used for the determination <strong>of</strong> both Na <strong>and</strong> K. In<br />
addition, the elemental relative concentration <strong>of</strong> the final U product was identified using (EDAX-<br />
SEM), PHILIPS <strong>and</strong> the product <strong>of</strong> Cu was identified using XRD technique PHILIPS, The pH value<br />
<strong>of</strong> the aqueous solutions were adjusted with a pH meter (Digimed DM-21).<br />
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<strong>Arab</strong> <strong>Journal</strong> <strong>of</strong> <strong>Nuclear</strong> <strong>Sciences</strong> <strong>and</strong> <strong>Applications</strong>, 45(2)169-178 (2012)<br />
2.3. Optimization <strong>of</strong> bioleaching parameters <strong>and</strong> recovery <strong>of</strong> Cu <strong>and</strong> U<br />
Bioleaching process upon the U <strong>and</strong> Cu bearing minerals <strong>of</strong> Abu Thor area was performed using<br />
A.Niger. The different bioleaching affecting factors such as: incubation period, (1-10 days), solid /<br />
liquid (S/L) ratio, (1/2 - 1/20), pH value (1- 8) <strong>and</strong> temperature, (25-100ºC) were investigated. The<br />
recovery <strong>of</strong> Cu was carried out by direct precipitation using the freshly released H2S while U was<br />
recovered <strong>and</strong> purified using 25% TBP in kerosene.<br />
Figure (1): Geological Map <strong>of</strong> Abu Thor Locality (Mira <strong>and</strong> Aita, 2009)<br />
3.1. Mineralogical <strong>and</strong> chemical composition<br />
3-RESULTS &DISCUSSION<br />
According to Mira <strong>and</strong> Aita (2009) (8) the mineralogical analysis <strong>of</strong> Abu Thor collected sample<br />
revealed the presence <strong>of</strong> different U <strong>and</strong> Cu minerals such as: zippeite,<br />
(K4(UO2)4(SO4)4(OH)10.4H2O) [Card No.,8-138], atacamite ,(Cu2Cl(OH)3) [Card No.,23-948],<br />
paratacamite (Cu2(OH)3Cl) [Card No.,23-947,] rosasite (Cu.Zn)2 CO3 (OH)2), [Card No.,17-216],<br />
calcite, (CaCO3 ) [Card No., 5-586], <strong>and</strong> dolomite, (CaMg(CO3)2. [Card No., 11-78]. On the other<br />
h<strong>and</strong>, the complete chemical analysis <strong>of</strong> the ore sample given in Table (1) revealed the presence <strong>of</strong><br />
0.22% U, 25% CuO, 33% SiO 2 <strong>and</strong>10%, Al2O3. In the mean time, some trace elements have been<br />
analyzed including Pb (80ppm) <strong>and</strong> Ni (10ppm).<br />
3.2. Optimization <strong>of</strong> bioleaching parameters<br />
As was expected, it was revealed from the color <strong>and</strong> the analysis <strong>of</strong> the bioleach liquor that Cu<br />
in parallel to U was effectively co-leached with A. Niger. Thus, it was decided to take the bioleaching<br />
<strong>of</strong> Cu in consideration with the different bioleaching parameters such as: incubation period, solid /<br />
liquid (S/L) ratio, pH values <strong>and</strong> temperature.<br />
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<strong>Arab</strong> <strong>Journal</strong> <strong>of</strong> <strong>Nuclear</strong> <strong>Sciences</strong> <strong>and</strong> <strong>Applications</strong>, 45(2)169-178 (2012)<br />
Table (1): Chemical composition <strong>of</strong> Abu Thor U bearing material.<br />
3.2.1. Effect <strong>of</strong> the incubation period.<br />
Major oxides Conc., (%) Trace<br />
elements<br />
Conc., ppm<br />
SiO 2 33 Na 4500<br />
Al2O3 10 Mn 1500<br />
CuO 25 K 1000<br />
CaO 8.5 U 2200<br />
MgO 2 V 1500<br />
Fe2O3 2 Pb 80<br />
1.3 Ni 10<br />
TiO 2<br />
P2O5<br />
1.5<br />
ZnO 2<br />
Total ignition loss 11.6<br />
This factor was studied by putting 100 ml <strong>of</strong> the Dox liquid medium in six 250 ml measuring<br />
flasks which were autoclaved at 1.5 atm. for 20min. After cooling, the flasks were inoculated with 0.5<br />
ml <strong>of</strong> spore suspension <strong>of</strong> A-Niger <strong>and</strong> finally incubated at 30ºC for 7 days. The flasks which contain<br />
the culture filtrate were supplemented with the ore sample at S/L ratio <strong>of</strong> 1/10 at pH <strong>of</strong> 3.5 <strong>and</strong> at 60ºC<br />
<strong>and</strong> incubated in an orbital shaker at 100 rpm. Both U <strong>and</strong> Cu were daily determined until reached the<br />
equilibrium stage. Triplicate sets <strong>of</strong> the fla sks for each day. Results in Table (2) indicated that both U<br />
<strong>and</strong> Cu leaching efficiencies were highly affected by the incubation time where the maximum leaching<br />
efficiencies attained 64% <strong>and</strong> 74%, respectively after 6 days. It was noticed that after 8 days the<br />
leaching percentage <strong>of</strong> U <strong>and</strong> Cu have together decreased. This phenomenon may be attributed to the<br />
effect <strong>of</strong> some interfering metal ions especially Zn, Fe <strong>and</strong> Al that might dissolved.<br />
3.2.2. Effect <strong>of</strong> Solid / Liquid (S/L) ratio.<br />
The effect <strong>of</strong> S/L ratio was performed by the addition <strong>of</strong> the culture filtrate <strong>of</strong> A. Niger which<br />
previously prepared to the ore sample at different S/L ratios namely: 1/2, 1/5,1/7, 1/10 <strong>and</strong>1/20. The<br />
flasks were incubated for 6days in an orbital shaker at 100rpm for 2 0min <strong>and</strong> filtrated. Both U <strong>and</strong><br />
Cu were analyzed <strong>and</strong> their leaching efficiencies were calculated <strong>and</strong> tabulated. It was noticed that<br />
the leaching efficiencies <strong>of</strong> the elements <strong>of</strong> interest increased by increasing S/L ratio. Where the<br />
leaching efficiency <strong>of</strong> U increased from 27 % to 74% <strong>and</strong> that <strong>of</strong> Cu increased from 21% to 64%, <strong>and</strong><br />
then started to decrease, Table (3).This may be attributed to sufficient <strong>of</strong> organic acids produced by<br />
A. Niger to soluble Cu <strong>and</strong> U beside the interfering elements e.g. Zn, Pb .<br />
Table (2): Effect <strong>of</strong> incubation periods upon U <strong>and</strong> Cu bioleaching efficiency.<br />
Days<br />
Leaching efficiency,%<br />
U Cu<br />
1 25 30<br />
2 28 53<br />
4 51 72<br />
6 74 64<br />
8 57 68<br />
10 52 65<br />
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Table (3): Effect S/L ratio upon U <strong>and</strong> Cu bioleaching efficiency.<br />
S/L Ratio<br />
Leaching efficiency,%<br />
U Cu<br />
1/2 27 21<br />
1/5 41 27<br />
1/7 51 38<br />
1/10 74 64<br />
1/20 68 61<br />
3.2.3. Effect <strong>of</strong> pH values<br />
The acidity <strong>of</strong> culture filtrate <strong>of</strong> A. Niger is one <strong>of</strong> the most important factors affecting the<br />
bioleaching <strong>of</strong> the working sample. However the culture was adjusted at different pH values; 1, 2,<br />
3.5, 6 <strong>and</strong> 8 <strong>and</strong> mixed with the ore sample at S/L ratio <strong>of</strong> 1/10 at room temperature <strong>and</strong> incubated for<br />
6 days. The data shown in Table (4) emphasized that, the maximum leaching efficiencies <strong>of</strong> U <strong>and</strong><br />
Cu, (87% <strong>and</strong> 77%, respectively) by culture filtrate <strong>of</strong> A. Niger was conducted by increasing the<br />
acidity <strong>of</strong> the culture filtrate up to pH1. It was found that, increasing the pH value <strong>of</strong> the culture<br />
filtrate has an opposite effect on the leaching efficiencies <strong>of</strong> Cu <strong>and</strong> U. This might be attributed to the<br />
role <strong>of</strong> medium acidity increase leads to more leaching <strong>of</strong> different elements.<br />
Table (4): Effect pH values upon U <strong>and</strong> Cu bioleaching efficiency.<br />
pH Values<br />
3.2.4. Effect <strong>of</strong> temperature.<br />
At the previous fixed conditions beyond varying the temperatures <strong>of</strong> culture filtrate <strong>of</strong> A. Niger<br />
from 25 ºC to 100 ºC. It was found that, both Cu <strong>and</strong> U leaching efficiencies increased by increasing<br />
temperature up to 60ºC where a subsequent decrease has been started. Results given in Table (5)<br />
indicated that, the maximum leaching efficiencies <strong>of</strong> both U <strong>and</strong> Cu (97% & 79%) were recorded at<br />
60ºC. The obtained results might be attributed to both autotrophic <strong>and</strong> heterotrophic microorganisms<br />
that are able to release Cu from chalcopyrite at temperature range from (60ºC - 80ºC) (Rossi,<br />
1990) (17) . Also, the rate <strong>of</strong> extraction <strong>of</strong> Cu at the temperature <strong>of</strong> 60ºC is much faster <strong>and</strong> economic<br />
(pradha et al., 2008) (18) .<br />
Table (5): Effect temperature upon U <strong>and</strong> Cu leaching efficiency.<br />
Temperature, ? C<br />
Leaching efficiency,%<br />
U Cu<br />
1 87 77<br />
2 75 74<br />
3.5 74 64<br />
6 53 35<br />
8 16 13<br />
Leaching efficiency,%<br />
U Cu<br />
30 74 64<br />
40 79 74<br />
60 97 79<br />
80 85 67<br />
100<br />
62<br />
53<br />
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From the previous study, it could be inferred that both U <strong>and</strong> Cu from Abu Thor representative<br />
sample clearly respond to bioleaching applications using culture filtrate <strong>of</strong> A. Niger incubated in 6 days<br />
at S/L ratio <strong>of</strong> 1/10 <strong>and</strong> adjusted to pH1 at 60 ºC.<br />
3.3. Recovery <strong>of</strong> Cu <strong>and</strong> U<br />
By applying the optimum conditions upon 100g <strong>of</strong> the ore sample yielded leach liquor contains<br />
0.19g/l U <strong>and</strong> 15.8g/l Cu with leaching efficiencies 86% <strong>and</strong> 79%, respectively. Also, the chemical<br />
analysis <strong>of</strong> the bioleach liquor revealed the presence <strong>of</strong> 0.63g/l Fe <strong>and</strong> 0.8g/l Zn with leaching<br />
efficiencies 45%<strong>and</strong> 56%, respectively. Copper was recovered from the bioleach liquor by direct<br />
precipitation with the addition <strong>of</strong> solid Na2S at pH value =1.5 due to the lower value <strong>of</strong> its solubility<br />
product with S -- anions namely: (Ksp CuS= 6.3 x 10 -36 <strong>and</strong> ZnS 2.5 x 10 -22 Alexeyev (1973) (19) . On the<br />
other h<strong>and</strong>, U 6+ <strong>and</strong> Fe 3+ were reduced with S -- anion to U 4+ <strong>and</strong> Fe 2+ .<br />
3.3.1. Direct precipitation <strong>of</strong> Cu<br />
Copper <strong>and</strong> zinc were directly precipitated as CuS <strong>and</strong> ZnS from the bioleach liquor <strong>of</strong> the ore<br />
material sample containing 15.8 g/l Cu, 0.8 g/l Zn besides 0.19 g/l U using the freshly prepared H2S<br />
gas with the addition <strong>of</strong> solid Na2S. The precipitation optimum conditions <strong>of</strong> CuS <strong>and</strong> ZnS were S/L<br />
ratio <strong>of</strong> 1/100, pH1.5 at room temperature. Practically, about 10g <strong>of</strong> Na2S (assays 68%) was added to<br />
1000ml <strong>of</strong> the bioleach liquor at pH1.5 at room temperature. After filtration <strong>and</strong> washing a weight<br />
22g <strong>of</strong> CuS was recovered with precipitation efficiency achieved 99%. The product was identified by<br />
using both XRD <strong>and</strong> EDAX techniques Figures (2,3), respectively. The purity <strong>of</strong> CuS achieved<br />
97.9% with impurities <strong>of</strong> 0.9% Zn, 0.3% Pb, 0.5% Mn <strong>and</strong> 0.4%Na.<br />
U 6+ + Cu 2+ + S -- ? CuS ? + U 4+ . + S<br />
3.3.2. Solvent extraction <strong>of</strong> U<br />
Black ppt<br />
The bioleach liquor containing 0.19g/l U <strong>and</strong> free <strong>of</strong> Cu <strong>and</strong> Zn was directed to the solvent<br />
extraction unit to recover U using 25% TBP in kerosene. However, 1200 ml <strong>of</strong> this solution was first<br />
treated with pellets NaOH to precipitate U 4+ at pH11.5 with precipitation efficiency <strong>of</strong> 96.5%. After<br />
filtration <strong>and</strong> washing, the impure U precipitate was completely dissolved in 3% HNO3 to have<br />
uranyl nitrate solution <strong>of</strong> pH0.6 <strong>and</strong> assaying 0.18g/l U. This solution was then treated with 25% TBP<br />
in kerosene at an O/A ratio <strong>of</strong> 1/1 <strong>and</strong> shaken for 5min where U was completely transferred to the<br />
organic phase. The loaded solvent was scrubbed with 1.5% HNO3 at an O/A ratio <strong>of</strong> 1/20 to minimize<br />
the co-extracted impurities such as: Fe, V <strong>and</strong> Zn.<br />
A solution <strong>of</strong> 8% Na2CO3 was therefore used for the stripping <strong>of</strong> U from the loaded solvent at an<br />
A/O ratio <strong>of</strong> 1/2 for a contact time <strong>of</strong> 5min with achieved stripping efficiency <strong>of</strong> 95%. U in the strip<br />
solution was crystallized by gentle evaporation at 70ºC <strong>and</strong> the obtained product was analyzed with<br />
SEM. The EDAX chart <strong>of</strong> the precipitate emphasized that it assays 99.3% <strong>of</strong> U, Figure (4). All the<br />
obtained data have been formulated into a worked follow-sheet shown schematically in Figure (5).<br />
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Card No. 6-0464<br />
CuS<br />
CuS<br />
4-CONCLUSIONS<br />
A successful bioleaching process with the culture filtrate <strong>of</strong> A.Niger was applied for leaching<br />
Cu <strong>and</strong> U from the representative ore material <strong>of</strong> Abu Thor area,(0.22% U & 20% Cu), West<br />
Sinai, Egypt with achieved leaching efficiencies <strong>of</strong> 97% <strong>and</strong> 79%, respectively. The bioleaching<br />
optimum conditions involve an incubation period <strong>of</strong> 6 days, S/L ratio <strong>of</strong> 1/10, <strong>and</strong> pH value <strong>of</strong>1<br />
<strong>and</strong> bioleaching temperature <strong>of</strong> 60ºC. The prepared leach liquor assaying15.8 g/l Cu <strong>and</strong> 0.19 g/l<br />
U was then directed to the direct precipitation both Cu <strong>and</strong> Zn impurities using the freshly<br />
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CuS<br />
CuS<br />
Figure (2): XRD pattern <strong>of</strong> the prepared pure CuS<br />
Figure (3): EDAX chart <strong>of</strong> the prepared pure CuS<br />
Figure (4): EDAX chart <strong>of</strong> the prepared pure pure yellow cake
<strong>Arab</strong> <strong>Journal</strong> <strong>of</strong> <strong>Nuclear</strong> <strong>Sciences</strong> <strong>and</strong> <strong>Applications</strong>, 45(2)169-178 (2012)<br />
prepared H2S gas which released by the addition <strong>of</strong> solid Na2S to the leach liquor. The optimum<br />
precipitation conditions have been included S/L ratio <strong>of</strong> 1/100, pH1.5 at room temperature. The<br />
achieved recovery <strong>of</strong> Cu as CuS reached 99.3% with purity 97.9% <strong>and</strong> co-precipitated impurities<br />
<strong>of</strong> 0.9 % Zn, 0.3% Pb, 0.5% Mn <strong>and</strong> 0.4%Na.<br />
The filtrate containing 0.19g/l <strong>of</strong> U was directed to the solvent extraction unit for recovering<br />
U using 25% TBP in kerosene. The maximum U extraction efficiency optimum conditions were<br />
O/A ratio <strong>of</strong> 1/1 <strong>and</strong> contact time <strong>of</strong> 5min. On the other h<strong>and</strong>, the stripping process was<br />
performed using 8% Na2CO3 solution at A/O ratio <strong>of</strong> 1/2 <strong>and</strong> contact time <strong>of</strong> 5min gave the<br />
maximum U stripping efficiency <strong>of</strong> 95%. The EDAX chart <strong>of</strong> the precipitate emphasized that it<br />
assays 99.3% U with total recovery achieved 86.36%.<br />
100g ore sample<br />
Culture filtrate<br />
S/L 1/10, pH1, 60 ? C<br />
H2O<br />
Washing<br />
CuS<br />
Filtrate<br />
Bioleaching<br />
Filtration<br />
Solid Na2S<br />
Cu precipitation<br />
S/L 1/100, pH=1.5, RT<br />
Filtration<br />
ppt<br />
Filtrate/ pH11<br />
Pellets NaOH<br />
Conc HNO3/pH0.6<br />
8% Na2CO3<br />
U precipitation<br />
Filtration<br />
-176-<br />
ppt<br />
Dissolution<br />
25% TBP<br />
Stripping<br />
U crystallization<br />
Pure Yellow cake<br />
Residue<br />
Figure (5): A worked follow-sheet for the processing <strong>of</strong> Abu Thor representative sample.
<strong>Arab</strong> <strong>Journal</strong> <strong>of</strong> <strong>Nuclear</strong> <strong>Sciences</strong> <strong>and</strong> <strong>Applications</strong>, 45(2)169-178 (2012)<br />
5-REFERENCES<br />
(1) Hilmy, M.E. <strong>and</strong> Mohsen, L.,(1965): (( Secondary copper minerals from West Central Sinai. )) , J.<br />
Geol. UAR 9, pp.1-12.<br />
(2) El Reedy, M.W.; Mahdy, M.A.; El Aassy, I.E <strong>and</strong> Dabbour, G.A.,(1988): (( Geochemistry<br />
studies <strong>of</strong> some uraniferous sedimentary rock varieties <strong>of</strong> West Central Sinai, Egypt. )) ,<br />
4 th Conf. Nuc.Sci. <strong>and</strong> Appl., Cairo, Egypt, V.1, pp. 224-229.<br />
(3) Dabbour, G.A. <strong>and</strong> Mahdy, M.A.,(1988) (( Mineralogical studies on the Carboniferous<br />
uraniferous sediments West Central Sinai, Egypt. )) 4 th Conf. Nuc. Sci. <strong>and</strong> Appl. Cairo,<br />
Egypt, V.1, pp. 230-237.<br />
(4) El Sharkawi, M.A., El Aref, M.M. <strong>and</strong> Abd El Motelib, A. 1990b: (( Syngenetic <strong>and</strong><br />
palaeokarstic copper mineralization in the Paleozoic platform sediments <strong>of</strong> West Central<br />
Sinai, Egypt. )) BL: Sediment- Hosted Mineral Deposits (Parnell, J. et al., eds.) Int. ASS.<br />
Sediments, pp. 159-172.<br />
(5) Hussein, H., Abd El Monem, A., Mahdy, M., El Aassy, I. <strong>and</strong> Dabbour, G., (1992): (( On the<br />
genesis <strong>of</strong> surficial uranium occurrences in West Central Sinai, Egypt )) . Ore Geol. Rev., V. 7,<br />
pp. 125-135.<br />
(6) Aita, S.K. (1996): (( Geological, mineralogical <strong>and</strong> geochemical studies on some radioactive<br />
anomalies <strong>of</strong> the Paleozoic sediments <strong>of</strong> Um Bogma area, West Central Sinai, Egypt. )) , M.Sc.<br />
Thesis, Cairo Univ., Egypt, p 262.<br />
(7) Abdel Monem, A.; El Aassy, I.E.; Hegab, O., El Fayoumy, I. <strong>and</strong> El Agami, N.,(1997):<br />
(( Gibbsite, uranium <strong>and</strong> copper mineralizations, Um Bogma area, Southwestern Sinai,<br />
Egypt )) , Sedim. <strong>of</strong> Egypt, V. 5, pp.117-132.<br />
(8) Mira. H. I., <strong>and</strong> Sami, S. K. (2009): (( Remobilization <strong>of</strong> U <strong>and</strong> Cu through karstification<br />
processes; a case study in Abu Thor locality, UmBogma region, West Central Sinai, Egypt ))<br />
Annals Geol. Surv. Egypt. V.XXXI<br />
(9) Akcil, A., (2004) (( Potential bioleaching developments towards commercial reality) ) Turkish<br />
metal mining future. Mineral Engineering, 17 (3) pp 477-480.<br />
(10) Gu, X. Y. <strong>and</strong> Wong, J. W., (2007) (( Degradation <strong>of</strong> inhibitory substances heterotrophic<br />
microorganisms during bioleaching <strong>of</strong> heavy metals from an aerobically digested sewage<br />
sludge )) Chemosphere, (22) pp11-15.<br />
(11) Hefnawy, M. A., Hashad, A., M <strong>and</strong> Maisa, A., (2003) (( Optimization <strong>of</strong> Uranium leaching<br />
parameters by A, terrous <strong>and</strong> p. spinulosum, African J, <strong>of</strong> mycology <strong>and</strong> biotechnology )) [1]<br />
pp 17-34.<br />
(12) Rawlings , D. E., (2004) (( Microbial assistant dissolution <strong>of</strong> minerals <strong>and</strong> its use in the mining<br />
industry )) pure App. Chem., 76, pp 847-859.<br />
(13) Youssef, H.I., (2007) (( Bioleaching <strong>of</strong> some heavy metals from different ores, Egypt )) , PhD<br />
Thesis, Faculty <strong>of</strong> Agriculture, Ain Shams University, Egypt.<br />
(14) Amer, T. E., (2007) (( Geochemical <strong>and</strong> extraction <strong>of</strong> U, Cu <strong>and</strong> Mn from the ore materials <strong>of</strong> the<br />
unifrous Paleozoic sedimentary rocks, West Central Sinai, Egypt )) , PhD Thesis, Faculty <strong>of</strong><br />
Science, Geology Department, Cairo University, Egypt.<br />
(15) Cecal, A., Humelnicu, D., Popa, K., Rudic, V., Gulea, A., Palamaru,I. <strong>and</strong> Nemtoi,G.,(2005)<br />
(( Bioleaching <strong>of</strong> UO2 2+ Ions from Poor Uranium Ores by Means <strong>of</strong> Cyanobacteria )) World<br />
<strong>Journal</strong> <strong>of</strong> Microbiology <strong>and</strong> Biotechnology, V21, No., 3, pp 377-380.<br />
-177-
<strong>Arab</strong> <strong>Journal</strong> <strong>of</strong> <strong>Nuclear</strong> <strong>Sciences</strong> <strong>and</strong> <strong>Applications</strong>, 45(2)169-178 (2012)<br />
(16) Daveis , W. <strong>and</strong> Gray, W. A.,(1964) (( Rapid <strong>and</strong> specific titrametric method for the precise<br />
determination <strong>of</strong> U using FeSO4 as reductant ) Talanta, 11,pp 1203-1211.<br />
(17) Raoosi, D.V., Shilvamavar, C, T. <strong>and</strong> Gadd, S. M., (2002) (( Bioleaching <strong>of</strong> copper from<br />
chalcolpyrite ore by fungi )) Indian J. Exp Biol. 40 (3) pp 319-324.<br />
(18) Pradhan, N., Mohapatra, S., Mohanty, S.<strong>and</strong> Sulka, L. B., (2008) (( Recovery <strong>of</strong> lateritic<br />
nickel ore using A.Niger <strong>and</strong> optimization parameters )) Minerals Engineering 1365, pp5674-<br />
5677.<br />
(19) Alexeyev, V.N., (1973) (( Qualitative Chemical Semi microanalysis )) , English translation, Mir<br />
Pub. 1980, pp. 210-215.<br />
-178-